Leveraging Exchange Kinetics for the Synthesis of Atomically Precise Porous Catalysts

Abstract

AbstractMetal‐organic frameworks (MOFs) have attracted significant attention as porous catalyst platforms due to the synthetic modularity of these materials and the diversity of lattice‐confined catalytic active sites that are readily embedded within periodic crystalline frameworks. MOFs offer platforms to heterogenize molecular catalysts, stabilize novel coordination motifs, and leverage confinement effects in catalysis. Crystallinity allows diffraction‐based methods to be employed in the characterization of these catalysts. Access to crystalline MOFs typically requires reversible construction of the metal−ligand (M−L) bonds that connect the SBUs, which provides a mechanism to anneal defects during crystallization. While the required M−L bond reversibility is often promoted by synthesis at elevated temperature, access to crystalline materials based on either transition metals with characteristic slow exchange kinetics or highly basic donor ligands remains a synthetic challenge. Here, we highlight synthetic strategies that leverage M−L exchange kinetics to access MOFs based on kinetically inert ions and extensions of these strategies to the assembly of atomically precise multimetallic materials.